KR101908866B1 - A solid catalyst for propylene polymerization and a method for preparation of polypropylene - Google Patents

A solid catalyst for propylene polymerization and a method for preparation of polypropylene Download PDF

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KR101908866B1
KR101908866B1 KR1020170162098A KR20170162098A KR101908866B1 KR 101908866 B1 KR101908866 B1 KR 101908866B1 KR 1020170162098 A KR1020170162098 A KR 1020170162098A KR 20170162098 A KR20170162098 A KR 20170162098A KR 101908866 B1 KR101908866 B1 KR 101908866B1
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ester
dicarboxylic acid
hept
ene
bicyclo
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KR1020170162098A
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Korean (ko)
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이영주
고수민
박한규
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한화토탈 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
    • C08F4/6545—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium and metals of C08F4/64 or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • C08F4/6491—Catalysts containing a specific non-metal or metal-free compound organic hydrocarbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention relates to a solid catalyst for propylene polymerization and a manufacturing method of polypropylene using the same, and provides a solid catalyst comprising a carrier generated through a reaction with dialkoxy magnesium and metal halide, titanium halide, an organic electron donor and the like, and a manufacturing method of polypropylene using the same. In particular, allyl group-substituted bicycloalkane among two types of organic electron donors, and an internal electron donor containing alkene dicarboxylate or bicycloalkane and alkene dicarboxamide are used in the present invention. Therefore, the solid catalyst of the present invention is able to be applied in propylene polymerization process in various forms such as a slurry polymerization method, a bulk polymerization or vapor-phase polymerization, and has a high activity, an excellent tacticity, and a high melt-flowability.

Description

프로필렌 중합용 고체촉매 및 이를 이용한 폴리프로필렌 제조방법{A SOLID CATALYST FOR PROPYLENE POLYMERIZATION AND A METHOD FOR PREPARATION OF POLYPROPYLENE}TECHNICAL FIELD [0001] The present invention relates to a solid catalyst for the polymerization of propylene, and a process for producing the same. BACKGROUND ART < RTI ID = 0.0 >

본 발명은 디알콕시마그네슘을 금속할라이드와의 반응을 통해서 생성된 담체와 티타늄할라이드, 유기전자공여체 등으로 이루어진 고체촉매 및 이를 이용한 폴리프로필렌 제조방법에 관한 것으로, 이러한 고체 촉매계로 이루어진 지글러-나타 촉매를 사용하여 프로필렌 중합체를 제조할 경우, 높은 입체규칙성을 갖는 폴리프로필렌 수지를 높은 수율로 제조할 수 있는 것이다.The present invention relates to a solid catalyst comprising a carrier formed by the reaction of a dialkoxy magnesium with a metal halide, a titanium halide, an organic electron donor and the like, and a process for producing a polypropylene using the solid catalyst. The Ziegler- It is possible to produce a polypropylene resin having a high stereoregularity with a high yield.

폴리프로필렌은 실생활에서나 상업적으로 매우 유용한 소재물질로, 특히 식품용기 등의 생활용품에서부터 자동차 및 전자제품 등에 널리 사용되고 있다. 이러한 폴리프로필렌의 다양한 제품성능을 위해서는 높은 결정화도를 통한 강성을 개선하는 것이 중요하며, 이를 위해서는 중합촉매의 역할이 무엇보다도 절실히 요구된다. 즉 생성되는 고분자의 입체규칙성을 향상시키도록 촉매시스템의 디자인이 수반되어야 한다. 이와 아울러 고분자 제조에 있어서의 경제성을 위해서는 촉매의 중합활성이 높을수록 더욱 유리하다. Polypropylene is a very useful material in real life and commercially, and is widely used especially in household goods such as food containers, automobiles and electronic products. For the performance of various polypropylene products, it is important to improve the rigidity through high crystallinity, and for this purpose, the role of polymerization catalyst is desperately required. That is, the design of the catalyst system must be accompanied to improve the stereoregularity of the resulting polymer. In addition, the higher the polymerization activity of the catalyst, the more advantageous it is for the economical efficiency in the production of the polymer.

한편 프로필렌의 기상중합, 슬러리 중합 및 벌크 중합에 사용되는 촉매계는 지글러-나타계 촉매 성분, 알킬알루미늄 및 외부전자공여체로 구성되어 있는 것이 일반적이다. 특히 이러한 촉매성분은 마그네슘, 티타늄, 및 내부전자공여체 및 할로겐을 필수성분으로서 함유하는 고체촉매로 알려져 있으며, 특히 내부 전자공여체는 분자구조에 따라 촉매의 활성 및 입체규칙성 등에 상당한 영향을 미치는 것으로 알려져 있다. 촉매 활성 증가를 통해 원가를 낮추고, 입체규칙성 등의 촉매 성능을 향상시켜 중합체의 물성을 개선시키기 위하여, 내부전자공여체로서 방향족 디카르복실산의 디에스테르를 사용하는 것은 보편적으로 널리 알려진 방법이며, 이에 관한 특허들이 출원되었다. 미국 특허 제4,562,173호, 미국 특허 제4,981,930호, 국내 특허 제0072844호 등은 그 예라고 할 수 있으며, 상기 특허들은 방향족 디알킬디에스테르 또는 방향족 모노알킬모노에스테르를 사용하여 고활성, 고입체규칙성을 발현하는 촉매 제조 방법을 소개하고 있다.On the other hand, the catalyst system used for gas phase polymerization, slurry polymerization and bulk polymerization of propylene is generally composed of a Ziegler-Natta catalyst component, alkyl aluminum and an external electron donor. Particularly, such a catalyst component is known as a solid catalyst containing magnesium, titanium, an internal electron donor and halogen as essential components, and it is known that the internal electron donor has a considerable influence on the activity and stereoregularity of the catalyst depending on the molecular structure have. It is a widely known method to use a diester of an aromatic dicarboxylic acid as an internal electron donor in order to lower the cost through the increase of the catalyst activity and to improve the property of the polymer by improving the catalytic performance such as stereoregularity, Patents related thereto were filed. U.S. Patent No. 4,562,173, U.S. Patent No. 4,981,930, and U.S. Patent No. 0072844, for example, disclose the use of aromatic dialkyl diesters or aromatic monoalkyl monoesters to produce high activity, In the presence of a catalyst.

상기 특허들의 방법은 고입체규칙성 중합체를 높은 수율로 얻기에는 충분히 만족스러운 것이 아니며 개선이 요구된다. The methods of these patents are not sufficiently satisfactory to obtain a high stereoregular polymer in high yield and require improvement.

국내　특허　제0491387호에는 비방향족인 디에테르 물질을, 국내 특허 제0572616호에는 비방향족이면서 케톤과 에테르 작용기를 동시에 가지는 물질을 내부전자공여체로 사용한 촉매 제조 방법이 개시되어 있다. 그러나, 이 두 방법 모두　활성과 입체규칙성 측면 모두에서 크게 개선되어야 할 여지가 있다. Korean Patent No. 0491387 discloses a non-aromatic diether material, and Korean Patent No. 0572616 discloses a method for producing a catalyst using a non-aromatic but simultaneously a ketone and an ether functional group as an internal electron donor. However, both of these methods need to be greatly improved in terms of both activity and stereoregularity.

또한 미국 특허 제2011/0040051호에는 디에틸 2,3-디이소프로필-2-시아노숙시네이트와 9,9-비스메톡시플로렌의 혼합물을 내부전자공여체로 사용하여 촉매를 제조하는 방법을 제안하고 있으나, 활성과 입체규칙성 측면 모두에서 매우 열세하여 개선이 요구되고 있다.U.S. Patent No. 2011/0040051 also discloses a method for preparing a catalyst by using a mixture of diethyl 2,3-diisopropyl-2-cyanosuccinate and 9,9-bismethoxyflorene as an internal electron donor However, it is very difficult to improve both in terms of activity and stereoregularity.

본 발명의 목적은 상기와 같은 종래기술들의 문제점을 해결하고자 하는 것으로, 높은 입체규칙성을 갖고 활성이 우수하면서도 높은 용융흐름성을 갖는 폴리프로필렌을 제조할 수 있는, 프로필렌 중합용 고체촉매 및 이를 이용한 폴리프로필렌 제조방법을 제공하는 것이다. It is an object of the present invention to solve the problems of the prior art as described above and to provide a solid catalyst for propylene polymerization which can produce polypropylene having high stereoregularity and high activity and high melt flowability, And to provide a method for producing polypropylene.

본 발명의 프로필렌 중합용 고체촉매의 제조방법은, 다음의 단계를 포함하여 이루어지는 것을 특징으로 한다.The method for producing a solid catalyst for propylene polymerization according to the present invention is characterized by comprising the following steps.

(1) 디에톡시마그네슘을 유기용매 존재하에서 금속할라이드 화합물과 비교적 낮은 온도에서 반응시키는 단계; (1) reacting diethoxy magnesium with a metal halide compound in the presence of an organic solvent at a relatively low temperature;

(2) 디에톡시마그네슘 반응 후 온도를 승온하면서 2종의 내부전자공여체를 반응시키는 단계;(2) reacting two internal electron donors while raising the temperature after diethoxy magnesium reaction;

(3) 높은 온도에서 일정시간동안 반응시키는 단계;(3) reacting at a high temperature for a predetermined time;

(4) 금속 할라이드 화합물과 높은 온도에서 2차로 반응시키고 이를 세척하는 단계.(4) reacting with the metal halide compound at a high temperature in a second step and washing it.

상기에 명시된 고체촉매의 제조공정에 있어서, (1)단계에서 사용된 디에톡시마그네슘은 금속마그네슘을 염화마그네슘의 존재하에서 무수알콜과 반응시켜 얻어지는 평균입경이 10~200㎛ 이고, 표면이 매끄러운 구형입자로서, 상기 구형의 입자형상은 프로필렌의 중합시에도 그대로 유지되는 것이 바람직한데, 상기 평균입경이 10㎛ 미만이면 제조된 촉매의 미세입자가 증가하여 바람직하지 않고, 200㎛를 초과하면 곁보기 밀도가 작아지고 촉매제조시 균일한 입자형상을 갖기 어려워 바람직하지 않다. In the process for producing a solid catalyst as described above, diethoxy magnesium used in the step (1) is a product obtained by reacting metallic magnesium with anhydrous alcohol in the presence of magnesium chloride and having an average particle size of 10 to 200 탆, It is preferable that the spherical shape of the particles is maintained as it is in polymerization of propylene. If the average particle diameter is less than 10 탆, the fine particles of the prepared catalyst are undesirably increased, and when the average particle diameter exceeds 200 탆, And it is difficult to have a uniform particle shape in the production of the catalyst, which is not preferable.

상기 (1)단계에서 사용되는 유기용매로서는, 그 종류에 특별한 제한이 없으며, 탄소수 6~12개의 지방족 탄화수소 및 방향족 탄화수소, 할로겐화 탄화수소 등이 사용될 수 있으며, 보다 바람직하게는 탄소수 7~10개의 포화 지방족 탄화수소 또는 방향족 탄화수소, 할로겐화 탄화수소가 사용될 수 있으며, 그 구체적인 예로는 헵탄, 옥탄, 노난, 데칸,톨루엔, 자일렌, 클로로헥산 및 클로로 헵탄 등으로부터 선택되는 1종 이상을 혼합하여 사용할 수 있다.The organic solvent used in the step (1) is not particularly limited and may be an aliphatic hydrocarbon having 6 to 12 carbon atoms, an aromatic hydrocarbon, a halogenated hydrocarbon or the like, more preferably a saturated aliphatic hydrocarbon having 7 to 10 carbon atoms A hydrocarbon, an aromatic hydrocarbon, or a halogenated hydrocarbon may be used. Specific examples thereof include at least one selected from heptane, octane, nonane, decane, toluene, xylene, chlorohexane and chloroheptane.

또한 상기 디에톡시마그네슘에 대한 상기 유기용매의 사용비는 디에톡시마그네슘 중량: 유기용매 부피로 1:5~1:50인 것이 바람직하며, 1:7 ~ 1:20 인 것이 보다 바람직한데, 상기 사용비가 1:5 미만이면 슬러리의 점도가 급격히 증가하여 균일한 교반이 어렵고, 1:50을 초과하면 생성되는 담체의 겉보기 밀도가 급격히 감소하거나 입자표면이 거칠어지는 문제가 발생하여 바람직하지 않다.Also, the use ratio of the organic solvent to the diethoxy magnesium is preferably 1: 5 to 1:50, more preferably 1: 7 to 1:20 by weight of diethoxy magnesium in terms of organic solvent volume, If the ratio is less than 1: 5, the viscosity of the slurry increases sharply and it is difficult to uniformly stir. When the ratio is more than 1:50, the bulk density of the carrier to be produced sharply decreases or the surface of the particles becomes rough.

상기 고체촉매의 제조과정에서 사용되는 티타늄 할라이드는 하기의 일반식 (I)로 표시할 수 있다:The titanium halide used in the preparation of the solid catalyst can be represented by the following general formula (I)

Ti(OR)nX(4-n) ………… (I)Ti (OR) n X (4-n) ... ... ... ... (I)

여기에서 R은 탄소원자 1~10개의 알킬기이고, X는 할로겐 원소를 나타내며, n은 일반식의 원자가를 맞추기 위한 것으로 0~3 의 정수이다. 구체적인 예로는 TiCl4, Ti(OCH3)Cl3,Ti(OC2H5)Cl3,Ti(OC3H7)Cl3, Ti(O(n-C4H9))Cl3, Ti(OCH3)2Cl2,Ti(OC2H5)2Cl2, Ti(OC3H7)2Cl2, Ti(O(n-C4H9))2Cl2, Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(OC3H7)3Cl, Ti(O(n-C4H9))3Cl 등이며, 이들 중 TiCl4가 바람직하게 사용된다. 또한 이들 4가 티타늄할라이드 화합물은 1종 단독 또는 2종 이상 조합하여 사용할 수도 있다. 상기 (1)단계의 반응 온도는 -10~60℃이다.Wherein R is an alkyl group having 1 to 10 carbon atoms, X is a halogen element, and n is an integer of 0 to 3 for matching the valency of the general formula. Specific examples include TiCl 4, Ti (OCH 3) Cl 3, Ti (OC 2 H 5) Cl 3, Ti (OC 3 H 7) Cl 3, Ti (O (nC 4 H 9)) Cl 3, Ti (OCH 3) 2 Cl 2, Ti ( OC 2 H 5) 2 Cl 2, Ti (OC 3 H 7) 2 Cl 2, Ti (O (nC 4 H 9)) 2 Cl 2, Ti (OCH 3) 3 Cl, Ti (OC 2 H 5 ) 3 Cl, Ti (OC 3 H 7 ) 3 Cl, and Ti (O (nC 4 H 9 )) 3 Cl. Of these, TiCl 4 is preferably used. These tetravalent titanium halide compounds may be used singly or in combination of two or more. The reaction temperature in step (1) is -10 to 60 ° C.

본 발명에 사용하는 2종의 유기전자공여체 중 알릴기가 치환된 바이시클로알칸 및 알켄디카르복실레이트계 또는 바이시클로 알칸 및 알켄디카복스아마이드가 포함된 내부전자공여체를 사용하는 것으로서 본 발명에서 제시하는 고체촉매는 슬러리 중합법, 벌크중합법 또는 기상중합법 등의 다양한 형태의 프로필렌 중합공정에 적용이 가능하며, 높은 활성과 입체규칙성이 우수하면서도 높은 용융흐름성을 갖는 프로필렌 수지를 제조할 수 있다.Among the two types of organic electron donors used in the present invention, the use of an internal electron donor including an allyl group-substituted bicycloalkane and an alkendicarboxylate-based or bicycloalkane and an alkenedicarboxamide, The solid catalyst can be applied to various types of propylene polymerization processes such as slurry polymerization, bulk polymerization or gas phase polymerization, and a propylene resin having a high activity and a high stereoregularity and a high melt flowability can be produced .

상기의 (2)단계에서 나타내는 2이상의 내부전자공여체 중 제1 내부전자공여체는 다음과 같은 일반식 (II), (III), (IV), (V), (VI), (VII), (VIII), (ⅠⅩ)로 표현되는 화합물들이다. The first inner electron donor among the two or more inner electron donors represented by the above step (2) may be represented by the following general formulas (II), (III), (IV), (V), (VI) VIII), (IX).

Figure 112017119347894-pat00001
Figure 112017119347894-pat00002
Figure 112017119347894-pat00001
Figure 112017119347894-pat00002

Figure 112017119347894-pat00003
Figure 112017119347894-pat00004
Figure 112017119347894-pat00003
Figure 112017119347894-pat00004

Figure 112017119347894-pat00005
Figure 112017119347894-pat00006
Figure 112017119347894-pat00005
Figure 112017119347894-pat00006

Figure 112017119347894-pat00007
Figure 112017119347894-pat00008

Figure 112017119347894-pat00007
Figure 112017119347894-pat00008

여기에서, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 은 서로 동일하거나 상이하고, 수소 및 탄소원자 1~30개의 포화 또는 불포화 고리형 알킬기, 알케닐기, 아릴기, 아릴알킬기 또는 알킬아릴기이고; R11, R12, R13 및 R14는 서로 동일하거나 상이하고, 수소, 탄소원자 1~20개의 선형, 가지형 또는 고리형 알킬기, 알케닐기, 아릴기, 아릴알킬기 또는 알킬아릴기이다.Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are the same or different and each is hydrogen or a saturated or unsaturated A cyclic alkyl group, an alkenyl group, an aryl group, an arylalkyl group or an alkylaryl group; R 11 , R 12 , R 13 and R 14 are the same or different and each is hydrogen, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aryl group, an arylalkyl group or an alkylaryl group.

즉 R11, R12, R13 , R14, R15,및 R16는 각각 독립적으로 탄소수 1∼12의 직쇄상 알킬기, 탄소수 3∼12의 분기 알킬기, 비닐기, 탄소수 3∼12의 직쇄상 알케닐기 또는 분기 알케닐기, 탄소수 1∼12의 직쇄상 할로겐 치환 알킬기, 탄소수 3∼12의 분기 할로겐 치환 알킬기, 탄소수 3∼12의 직쇄상 할로겐 치환 알케닐기 또는 분기 할로겐 치환 알케닐기, 탄소수3∼12의 시클로알킬기, 탄소수 3∼12의 시클로알케닐기, 탄소수 3∼12의 할로겐 치환 시클로알킬기, 탄소수 3∼12의 할로겐 치환 시클로알케닐기, 또는 탄소수 6∼12의 방향족 탄화수소기이며, 더욱 바람직한 기는, 탄소수 1∼12의 직쇄상 알킬기, 탄소수 3∼12의 분기 알킬기, 비닐기, 탄소수 3∼12의 직쇄상 알케닐기 또는 분기 알케닐기, 탄소수 1∼12의 직쇄상 할로겐 치환 알킬기, 탄소수 3∼12의 분기 할로겐 치환 알킬기, 탄소수 3∼12의 시클로알킬기, 탄소수 3∼12의 시클로알케닐기, 또는 탄소수 6∼12의 방향족 탄화수소기이며, 특히 바람직한 기는, 탄소수 1∼12의 직쇄상 알킬기, 탄소수 3∼12의 분기 알킬기, 및 탄소수 6∼12의 환형 탄화수소기이다.R 11 , R 12 , R 13 , R 14 , R 15 and R 16 each independently represent a straight chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a straight chain A straight chain halogenated alkyl group having 1 to 12 carbon atoms, a branched halogenated alkyl group having 3 to 12 carbon atoms, a straight chain halogenated alkenyl group having 3 to 12 carbon atoms, or a branched halogenated alkenyl group having 3 to 12 carbon atoms, A cycloalkyl group having 3 to 12 carbon atoms, a halogen-substituted cycloalkyl group having 3 to 12 carbon atoms, a halogen-substituted cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a cycloalkyl group having 3 to 12 carbon atoms, A straight chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a straight chain alkenyl group or a branched alkenyl group having 3 to 12 carbon atoms, a straight chain halogenated alkyl group having 1 to 12 carbon atoms, Halogen value An alkyl group, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, particularly preferably a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms , And a cyclic hydrocarbon group having 6 to 12 carbon atoms.

그 구체적인 예로는, 비시클로[2.2.1]헵탄-2,3-디카르복실산디페닐에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1-메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2-메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(3-메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(4-메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(5-메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2-디메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3-디메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,4-디메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(4,5-디메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,3-디메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,4-디메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,5-디메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,4-디메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,5-디메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,5-디메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2-디에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3-디에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,4-디에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(4,5-디에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,3-디에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,4-디에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,5-디에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,4-디에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,5-디에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,5-디에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,4-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(4,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,3-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,4-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,4-디-n-프로필페닐)에스테르,비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,4-디-iso-프로필페닐)에스테르,비시클로[2.2.1]헵탄-2,3-디카르복실산디(4,5-디-iso-프로필페닐)에스테르,비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,3-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,4-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,5-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,4-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,5-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,5-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,3-트리메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,4-트리메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,5-트리메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,4-트리메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,5-트리메틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,3-트리에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,4-트리에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,5-트리에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,4-트리에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,5-트리에틸페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,3-트리-n-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,4-n-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,5-n-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,4-n-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,5-n-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,3-트리-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,4-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,5-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,4--iso-프로필페닐)에스테르, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,5--iso-프로필페닐)에스테르, 7,7-디 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1-메틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2-메틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵탄-2,3-디카르복실산디(3-메틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵탄-2,3-디카르복실산디(4-메틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵탄-2,3-디카르복실산디(5-메틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2-디메틸페닐)에스테르,7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3-디메틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,4-디메틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(4,5-디메틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,3-디메틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,4-디메틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,5-디메틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,4-디메틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,5-디메틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,5-디메틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2-디에틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3-디에틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,4-디에틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(4,5-디에틸페닐)에스테르,7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,3-디에틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,4-디에틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,5-디에틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,4-디에틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,5-디에틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,5-디에틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2-디-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3-디-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,4-디-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(4,5-디-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,3-디-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,4-디-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,5-디-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,4-디-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,5-디-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,5-디-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2-디-iso-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3-디-iso-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,4-디-iso-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(4,5-디-iso-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,3-디-iso-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,4-디-iso-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,5-디-iso-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,4-디-iso-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,5-디-iso-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(3,5-디-iso-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,3-트리메틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,4-트리메틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,5-트리메틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,4-트리메틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,5-트리메틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,3-트리에틸페닐)에스테르,7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,4-트리에틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,5-트리에틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,4-트리에틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,5-트리에틸페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,3-트리-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,4-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,5-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,4-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,5-n-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,3-트리-iso-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,4-iso-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2,5-iso-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,4-iso-프로필페닐)에스테르, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(2,3,5-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디페닐에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1-메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2-메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3-메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(4-메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(5-메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2-디메틸페닐)에스테르,비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,4-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(4,5-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,3-디메틸페닐)에스테르,비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,4-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,5-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,4-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,5-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,5-디메틸페닐)에스테르,비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2-디에틸페닐)에스테르,비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,4-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(4,5-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,3-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,4-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,5-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,4-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,5-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,5-디에틸페닐)에스테르,비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2-디-n-프로필페닐)에스테르,비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,4-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(4,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,3-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,4-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,4-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,4-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(4,5-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,3-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,4-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,5-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,4-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,5-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,5-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,3-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,4-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,5-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,4-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,5-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,3-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,4-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,5-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,4-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,5-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,3-트리-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,4-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,5-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,4-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,5-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,3-트리-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,4-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,5-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,4--iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,5--iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1-메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2-메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3-메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(4-메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(5-메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,4-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(4,5-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,3-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,4-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,5-디메틸페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,4-디메틸페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,5-디메틸페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,5-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,4-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(4,5-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,3-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,4-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,5-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,4-디에틸페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,5-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,5-디에틸페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,4-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(4,5-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,3-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,4-디-n-프로필페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,5-디-n-프로필페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,4-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,5-디-n-프로필페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,5-디-n-프로필페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,4-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(4,5-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,3-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,4-디-iso-프로필페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,5-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,4-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,5-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(3,5-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,3-트리메틸페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,4-트리메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,5-트리메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,4-트리메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,5-트리메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,3-트리에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,4-트리에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,5-트리에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,4-트리에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,5-트리에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,3-트리-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,4-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,5-n-프로필페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,4-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,5-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,3-트리-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,4-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(1,2,5-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,4-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디(2,3,5-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디페닐에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1-메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2-메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3-메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(4-메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(5-메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,4-디메틸페닐)에스테르,비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(4,5-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,3-디메틸페닐)에스테르,비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,4-디메틸페닐)에스테르,비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,5-디메틸페닐)에스테르,비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,4-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,5-디메틸페닐)에스테르,비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,5-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,4-디에틸페닐)에스테르,비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(4,5-디에틸페닐)에스테르,비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,3-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,4-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,5-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,4-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,5-디에틸페닐)에스테르,비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,5-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,4-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(4,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,3-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,4-디-n-프로필페닐)에스테르,비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,4-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,4-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(4,5-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,3-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,4-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,5-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,4-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,5-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,5-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,3-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,4-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,5-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,4-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,5-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,3-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,4-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,5-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,4-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,5-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,3-트리-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,4-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,5-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,4-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,5-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,3-트리-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,4-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,5-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,4--iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,5--iso-프로필페닐)에스테르, 7,7-디 메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1-메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2-메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3-메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(4-메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(5-메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,4-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(4,5-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,3-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,4-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,5-디메틸페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,4-디메틸페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,5-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,5-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,4-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(4,5-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,3-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,4-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,5-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,4-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,5-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,5-디에틸페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,4-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(4,5-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,3-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,4-디-n-프로필페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,5-디-n-프로필페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,4-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,5-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,5-디-n-프로필페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,4-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(4,5-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,3-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,4-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,5-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,4-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,5-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(3,5-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,3-트리메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,4-트리메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,5-트리메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,4-트리메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,5-트리메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,3-트리에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,4-트리에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,5-트리에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,4-트리에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,5-트리에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,3-트리-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,4-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,5-n-프로필페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,4-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,5-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,3-트리-iso-프로필페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,4-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(1,2,5-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,4-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복실산디(2,3,5-iso-프로필페닐)에스테르,비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디페닐에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1-메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2-메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3-메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(4-메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(5-메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,4-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(4,5-디메틸페닐)에스테르,비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,3-디메틸페닐)에스테르,비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,4-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,5-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,4-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,5-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,5-디메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,4-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(4,5-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,3-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,4-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,5-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,4-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,5-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,5-디에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,4-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(4,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,3-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,4-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,4-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,5-디-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,4-디-iso-프로필페닐)에스테르,비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(4,5-디-iso-프로필페닐)에스테르,비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,3-디-iso-프로필페닐)에스테르,비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,4-디-iso-프로필페닐)에스테르,비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,5-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,4-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디 엔-2,3-디카르복실산디(2,5-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,5-디-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,3-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,4-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,5-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,4-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,5-트리메틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,3-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,4-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,5-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,4-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,5-트리에틸페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,3-트리-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,4-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,5-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,4-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,5-n-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,3-트리-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,4-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,5-iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,4--iso-프로필페닐)에스테르, 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,5--iso-프로필페닐)에스테르, 7,7-디 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1-메틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2-메틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3-메틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(4-메틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(5-메틸페닐)에스테르, 7,7-디 비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,4-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(4,5-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,3-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,4-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,5-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,4-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,5-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,5-디메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3-디에틸페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,4-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(4,5-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,3-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,4-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,5-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,4-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,5-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,5-디에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,4-디-n-프로필페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(4,5-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,3-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,4-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,5-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,4-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,5-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,5-디-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,4-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(4,5-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,3-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,4-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,5-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,4-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,5-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(3,5-디-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,3-트리메틸페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,4-트리메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,5-트리메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,4-트리메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,5-트리메틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,3-트리에틸페닐)에스테르,7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,4-트리에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,5-트리에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,4-트리에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,5-트리에틸페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,3-트리-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,4-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,5-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,4-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,5-n-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,3-트리-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,4-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(1,2,5-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,4-iso-프로필페닐)에스테르, 7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복실산디(2,3,5-iso-프로필페닐)에스테르,N2,N2,N3,N3-테트라메틸비시클로[2.2.1]헵탄-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-7,7-디메틸비시클로[2.2.1]헵탄-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-5-메틸비시클로[2.2.1]헵탄-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-5,6-디메틸비시클로[2.2.1]헵탄-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-5-메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-6-메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-5,6-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-5,6-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복스아마이드,N2,N2,N3,N3-테트라메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-5-메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-6-메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-5,6-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-5,6-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복스아마이드,N2,N2,N3,N3-테트라메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-5-메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-6-메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복스아마이드,N2,N2,N3,N3-테트라메틸-5,6-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라메틸-5,6-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복스아마이드,N2,N2,N3,N3-테트라에틸비시클로[2.2.1]헵탄-2,3-디카르복스아마이드,N2,N2,N3,N3-테트라에틸-7,7-디메틸비시클로[2.2.1]헵탄-2,3-디카르복스아마이드,N2,N2,N3,N3-테트라에틸-5-메틸비시클로[2.2.1]헵탄-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라에틸-5,6-디메틸비시클로[2.2.1]헵탄-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라에틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라에틸-7,7-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라에틸-5-메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라에틸-6-메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라에틸-5,6-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라에틸-5,6-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복스아마이드,N2,N2,N3,N3-테트라에틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라에틸-7,7-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라에틸-5-메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라에틸-6-메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라에틸-5,6-디에틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라에틸-5,6-디메틸비시클로[2.2.1]헵트-2-엔-2,3-디카르복스아마이드,N2,N2,N3,N3-테트라에틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라에틸-7,7-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복스아마이드,N2,N2,N3,N3-테트라에틸-5-메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복스아마이드,N2,N2,N3,N3-테트라에틸-6-메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복스아마이드,N2,N2,N3,N3-테트라에틸-5,6-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복스아마이드, N2,N2,N3,N3-테트라에틸-5,6-디메틸비시클로[2.2.1]헵트-2,5-디엔-2,3-디카르복스아마이드 등이 있다.Specific examples thereof include bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid diphenyl ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (1-methylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2-methylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (3-methylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (4-methylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (5-methylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (1,2-dimethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (2,3-dimethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (3,4-dimethylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (4,5-dimethylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,3-dimethylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,4-dimethylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,5-dimethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (2,4-dimethylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,5-dimethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (3,5-dimethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (1,2-diethylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3-diethylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (3,4-diethylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (4,5-diethylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,3-diethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (1,4-diethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (1,5-diethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (2,4-diethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (2,5-diethylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (3,5-diethylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2-di-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3-di-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (3,4-di-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (4,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,3-di-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,4-di-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,4-di-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (3,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2-di-isopropylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3-di-isopropylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (3,4-di-isopropylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (4,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,3-di-isopropylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,4-di-isopropylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,4-di-isopropylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (3,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2,3-trimethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (1,2,4-trimethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (1,2,5-trimethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (2,3,4-trimethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (2,3,5-trimethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (1,2,3-triethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (1,2,4-triethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (1,2,5-triethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (2,3,4-triethylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3,5-triethylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (1,2,3-tri-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2,4-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2,5-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3,4-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3,5-n-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2,3-tri-iso-propylphenyl) ester, bicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2,4-isopropylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (1,2,5-isopropylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (2,3,4-isopropylphenyl) ester, bicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (2,3,5-isopropylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1-methylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2-methylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (3-methylphenyl) ester, 7,7-dibicyclo [2.. 2. 1] heptane-2,3-dicarboxylic acid di (4-methylphenyl) ester, 7,7-dibicyclo [2.. 2. 1] heptane-2,3-dicarboxylic acid di (5-methylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2-dimethylphenyl) ester, 7,7-dibicyclo [2. 2. 1] heptane-2,3-dicarboxylic acid di (2,3-dimethylphenyl) ester, 7,7-dibicyclo [2.. 2. 1] heptane-2,3-dicarboxylic acid di (3,4-dimethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (4,5-dimethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,3-dimethylphenyl) ester, 7,7-dibicyclo [2.. 2. 1] heptane-2,3-dicarboxylic acid di (1,4-dimethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,5-dimethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,4-dimethylphenyl) ester, 7,7-dibicyclo [2.. 2. 1] heptane-2,3-dicarboxylic acid di (2,5-dimethylphenyl) ester, 7,7-dibicyclo [2.. 2. 1] heptane-2,3-dicarboxylic acid di (3,5-dimethylphenyl) ester, 7,7-dibicyclo [2.. 2. 1] heptane-2,3-dicarboxylic acid di (1,2-diethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3-diethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (3,4-diethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (4,5-diethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,3-diethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,4-diethylphenyl) ester, 7,7-dibicyclo [2.. 2. 1] heptane-2,3-dicarboxylic acid di (1,5-diethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,4-diethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,5-diethylphenyl) ester, 7,7-dibicyclo [2.. 2. 1] heptane-2,3-dicarboxylic acid di (3,5-diethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2-di-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3-di-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (3,4-di-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (4,5-di-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,3-di-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,4-di-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,5-di-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,4-di-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,5-di-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (3,5-di-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2-di-isopropylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3-di-isopropylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (3,4-di-isopropylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (4,5-di-isopropylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,3-di-isopropylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,4-di-isopropylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,5-di-isopropylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,4-di-isopropylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,5-di-isopropylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (3,5-di-isopropylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2,3-trimethylphenyl) ester, 7,7-dibicyclo [2.. 2. 1] heptane-2,3-dicarboxylic acid di (1,2,4-trimethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2,5-trimethylphenyl) ester, 7,7-dibicyclo [2.. 2. 1] heptane-2,3-dicarboxylic acid di (2,3,4-trimethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3,5-trimethylphenyl) ester, 7,7-dibicyclo [2.. 2. 1] heptane-2,3-dicarboxylic acid di (1,2,3-triethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2,4-triethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2,5-triethylphenyl) ester, 7,7-dibicyclo [2.. 2. 1] heptane-2,3-dicarboxylic acid di (2,3,4-triethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3,5-triethylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2,3-tri-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2,4-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2,5-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3,4-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3,5-n-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2,3-tri-iso-propylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (1,2,4-isopropylphenyl) ester, 7,7-dibicyclo [2.. 2. 1] heptane-2,3-dicarboxylic acid di (1,2,5-isopropylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3,4-isopropylphenyl) ester, 7,7-dibicyclo [ 2. 1] heptane-2,3-dicarboxylic acid di (2,3,5-iso-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid diphenyl ester, bicyclo [2. 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1-methylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2-methylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3-methylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (4-methylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (5-methylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2-dimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3-dimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,4-dimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (4,5-dimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,3-dimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,4-dimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,5-dimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,4-dimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,5-dimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,5-dimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2-diethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3-diethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,4-diethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (4,5-diethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,3-diethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,4-diethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,5-diethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,4-diethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,5-diethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,5-diethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,4-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (4,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,3-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,4-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,4-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,4-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (4,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,3-di-iso-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,4-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,5-di-iso-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,4-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,3-trimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,4-trimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,5-trimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,4-trimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,5-trimethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,3-triethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,4-triethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,5-triethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,4-triethylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,5-triethylphenyl) ester, bicyclo [2. 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,3-tri-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,4-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,5-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,4-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,5-n-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,3-tri-iso-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,4-isopropylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,5-iso-propylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,4-isopropylphenyl) ester, bicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,5-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1-methylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2-methylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3-methylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (4-methylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (5-methylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,4-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (4,5-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,3-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,4-dimethylphenyl) ester, 7,7-dimethylbicyclo [2. 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,5-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,4-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,5-dimethylphenyl) ester, 7,7-dimethylbicyclo [2.. 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,5-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,4-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (4,5-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,3-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,4-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,5-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,4-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,5-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,5-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3-di-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,4-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (4,5-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,3-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,4-di-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,5-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,4-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,5-di-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,5-di-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,4-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (4,5-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,3-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,4-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,5-di-isopropylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,4-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,5-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (3,5-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,3-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,4-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,5-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,4-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,5-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,3-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,4-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,5-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,4-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,5-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,3-tri-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,4-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,5-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,4-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,5-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,3-triisopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,4-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (1,2,5-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,4-isopropylphenyl) ester, 7,7-dimethylbicyclo [2.. 2. 1] hept-5-ene-2,3-dicarboxylic acid di (2,3,5-iso-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid diphenyl ester, bicyclo [2. 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1-methylphenyl) ester, bicyclo [2. 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2-methylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylate (3-methylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (4-methylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (5-methylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,4-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (4,5-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,3-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,4-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,5-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,4-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,5-dimethylphenyl) ester, bicyclo [2. 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,5-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2-diethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3-diethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,4-diethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (4,5-diethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,3-diethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,4-diethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,5-diethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,4-diethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,5-diethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,5-diethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,4-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (4,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,3-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,4-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,4-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,4-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (4,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,3-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,4-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,4-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,3-trimethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,4-trimethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,5-trimethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,4-trimethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,5-trimethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,3-triethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,4-triethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,5-triethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,4-triethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,5-triethylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,3-tri-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,4-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,5-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,4-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,5-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,3-tri-iso-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,4-isopropylphenyl) ester, bicyclo [2. 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,5-iso-propylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,4-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,5-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylate (1-methylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2-methylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3-methylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (4-methylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (5-methylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,4-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (4,5-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,3-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,4-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,5-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,4-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,5-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,5-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,4-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (4,5-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylate di (1,3-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,4-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,5-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,4-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,5-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,5-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,4-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (4,5-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,3-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,4-di-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,5-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,4-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,5-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,5-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,4-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (4,5-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,3-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,4-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,5-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,4-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,5-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (3,5-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,3-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,4-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,5-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,4-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,5-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,3-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,4-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,5-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,4-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,5-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,3-tri-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,4-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,5-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,4-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,5-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,3-triisopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,4-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (1,2,5-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,4-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2-ene-2,3-dicarboxylic acid di (2,3,5-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid diphenyl ester, bicyclo [2. 2. 1] hept-2,5-diene-2,3-dicarboxylate (1-methylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2-methylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3-methylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (4-methylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (5-methylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,4-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (4,5-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,3-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,4-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,5-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,4-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,5-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,5-dimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2-diethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3-diethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,4-diethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (4,5-diethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,3-diethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,4-diethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,5-diethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,4-diethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,5-diethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,5-diethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,4-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (4,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,3-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,4-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,4-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,5-di-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,4-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (4,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,3-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,4-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,4-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,5-di-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,3-trimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,4-trimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,5-trimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,4-trimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,5-trimethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,3-triethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,4-triethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,5-triethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,4-triethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,5-triethylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,3-tri-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,4-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,5-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,4-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,5-n-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,3-triisopropylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,4-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,5-iso-propylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,4-isopropylphenyl) ester, bicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,5-isopropylphenyl) ester, 7,7-dibicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1-methylphenyl) ester, 7,7-dibicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2-methylphenyl) ester, 7,7-dibicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3-methylphenyl) ester, 7,7-dibicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (4-methylphenyl) ester, 7,7-dibicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (5-methylphenyl) ester, 7,7-dibicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,4-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (4,5-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,3-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,4-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,5-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,4-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,5-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,5-dimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,4-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (4,5-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,3-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,4-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,5-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,4-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,5-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,5-diethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2-di-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,4-di-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (4,5-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,3-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,4-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,5-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,4-di-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,5-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,5-di-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,4-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (4,5-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,3-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,4-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,5-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,4-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,5-di-isopropylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (3,5-di-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,3-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,4-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,5-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,4-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,5-trimethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,3-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,4-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,5-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,4-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,5-triethylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,3-tri-n-propylphenyl) ester and 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,4-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,5-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,4-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,5-n-propylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,3-triisopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,4-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (1,2,5-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,4-isopropylphenyl) ester, 7,7-dimethylbicyclo [ 2. 1] hept-2,5-diene-2,3-dicarboxylic acid di (2,3,5-iso-propylphenyl) 2 , N 2 , N 3 , N 3 - tetramethylbicyclo [2.2.1] heptane-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetramethyl-7,7-dimethylbicyclo [2.2.1] heptane-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetramethyl-5-methylbicyclo [2.2.1] heptane-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetramethyl-5,6-dimethylbicyclo [2.2.1] heptane-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetramethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 -Tetramethyl-7,7-dimethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 -Tetramethyl-5-methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetramethyl-6-methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 -Tetramethyl-5,6-dimethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 -Tetramethyl-5,6-dimethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetramethylbicyclo [2.2.1] hept-2-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 -Tetramethyl-7,7-dimethylbicyclo [2.2.1] hept-2-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 -Tetramethyl-5-methylbicyclo [2.2.1] hept-2-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 -Tetramethyl-6-methylbicyclo [2.2.1] hept-2-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 -Tetramethyl-5,6-dimethylbicyclo [2.2.1] hept-2-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 -Tetramethyl-5,6-dimethylbicyclo [2.2.1] hept-2-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetramethylbicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetramethyl-7,7-dimethylbicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 -Tetramethyl-5-methylbicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetramethyl-6-methylbicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 -Tetramethyl-5,6-dimethylbicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 -Tetramethyl-5,6-dimethylbicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethylbicyclo [2.2.1] heptane-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-7,7-dimethylbicyclo [2.2.1] heptane-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-5-methylbicyclo [2.2.1] heptane-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-5,6-dimethylbicyclo [2.2.1] heptane-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-7,7-dimethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-5-methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-6-methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-5,6-dimethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-5,6-dimethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethylbicyclo [2.2.1] hept-2-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-7,7-dimethylbicyclo [2.2.1] hept-2-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-5-methylbicyclo [2.2.1] hept-2-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-6-methylbicyclo [2.2.1] hept-2-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-5,6-diethylbicyclo [2.2.1] hept-2-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-5,6-dimethylbicyclo [2.2.1] hept-2-ene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethylbicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-7,7-dimethylbicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-5-methylbicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-6-methylbicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 - tetraethyl-5,6-dimethylbicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxamide, N 2 , N 2 , N 3 , N 3 -Tetraethyl-5,6-dimethylbicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxamide, and the like.

한편 제2내부전자공여체는 특별한 제한은 없으며, 따라서 알코올류, 에테르류, 케톤류, 카르복실산류 등과 같이 올레핀 중합용 지글러계 촉매의 제조에 내부전자공여체로서 사용가능한 화합물이라면 제한없이 사용가능하지만, 그 중에서도 카르복실산 화합물을 사용하는 것이 바람직하고, 벤젠-1,2-디카르복실산에스테르 화합물로부터 선택된 하나 또는 그 이상을 혼합하여 제2내부전자공여체로서 사용하는 것이 더욱 바람직하다. 상기 벤젠-1,2-디카르복실산에스테르 화합물의 구체적인 예로는, 디메틸프탈레이트, 디에틸프탈레이트, 디노말프로필프탈레이트, 디이소프로필프탈레이트, 디노말부틸프탈레이트, 디이소부틸프탈레이트 디노말펜틸프탈레이트, 디(2-메틸부틸)프탈레이트, 디(3-메틸부틸)프탈레이트, 디(3-메틸펜틸)프탈레이트, 디이소헥실프탈레이트, 디네오헥실프탈레이트, 디(2,3-디메틸부틸)프탈레이트, 디이소헥실프탈레이트, 디네오헥실프탈레이트, 디(2,3-디메틸부틸)프탈레이트, 디노말헵틸프탈레이트, 디(2-메틸헥실)프탈레이트, 디(2-에틸펜틸)프탈레이트, 디이소헵틸프탈레이트, 디네오헵틸프탈레이트, 디노말옥틸프탈레이트, 디(2-메틸헵틸)프탈레이트, 디이소옥틸프탈레이트, 디(3-에틸헥실)프탈레이트, 디네오옥틸프탈레이트, 디노말노닐프탈레이트, 디이소노닐프탈레이트, 디노말데실프탈레이트, 디이소데실프탈레이트 등을 들 수 있다.The second internal electron donor is not particularly limited and can be used without limitation as long as it is a compound that can be used as an internal electron donor in the production of a Ziegler-based catalyst for olefin polymerization such as alcohols, ethers, ketones, and carboxylic acids. It is preferable to use a carboxylic acid compound, and it is more preferable to use a mixture of one or more selected from benzene-1,2-dicarboxylic acid ester compounds as a second internal electron donor. Specific examples of the benzene-1,2-dicarboxylic acid ester compound include dimethyl phthalate, diethyl phthalate, dinompropyl phthalate, diisopropyl phthalate, dinomal butyl phthalate, diisobutyl phthalate dinomentyl phthalate, di (2-methylbutyl) phthalate, di (3-methylbutyl) phthalate, di (3-methylpentyl) phthalate, diisobutylphthalate, dineohexylphthalate, di (2-ethylhexyl) phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-n-hexyl phthalate, dibutyl phthalate, , Di (2-methylheptyl) phthalate, diisooctyl phthalate, di (3-ethylhexyl) phthalate, dineoctyl phthalate, dinononyl phthalate, di Carbonyl phthalate, and the like Dino end decyl phthalate, diisodecyl phthalate.

한편 제2 내부전자공여체로는 1,3-디에테르류의 사용도 매우 바람직하며, 다음의 일반식 (X)와 같은 구조로 표현되는 화합물이 매우 바람직하다. On the other hand, as the second internal electron donor, the use of 1,3-diethers is also very preferable, and compounds represented by the following formula (X) are very preferable.

R6R7C(CH2OR8)(CH2OR9)‥‥‥ (X)R 6 R 7 C (CH 2 OR 8 ) (CH 2 OR 9 ) (X)

식 중, R6 및 R7는 동일하거나 상이하고, C1-C18 알킬, C3-C18 시클로알킬 또는 C7-C18 아릴 라디칼이고; R8 및 R9는 동일하거나 상이하고, C1-C4 알킬 라디칼이거나; 위치 2의 탄소 원자가, 2 또는 3 개의 불포화를 함유하고 탄소수 5, 6 또는 7 로 이루어진 시클릭 또는 폴리시클릭에 속하는 1,3-디에테르류이다.Wherein R 6 and R 7 are the same or different and are C 1 -C 18 alkyl, C 3 -C 18 cycloalkyl or C 7 -C 18 aryl radical; R 8 and R 9 are the same or different and are a C 1 -C 4 alkyl radical; The carbon atom at position 2 is a 1,3-diether containing cyclic or polycyclic, containing 2 or 3 unsaturations and consisting of 5, 6 or 7 carbon atoms.

상기 단계 (2)은 상기 단계 (1)의 결과물의 온도를 60~150℃, 바람직하게는 80~130℃까지 서서히 승온시키면서, 승온 과정 중에 내부전자공여체를 투입하여 1~3시간 동안 반응시킴으로써 수행되는 것이 바람직한데, 상기 온도가 60℃ 미만이거나 반응시간이 1시간 미만이면 반응이 완결되기 어렵고, 상기 온도가 150℃를 초과하거나 반응시간이 3시간을 초과하면 부반응에 의해 결과물인 촉매의 중합활성 또는 중합체의 입체규칙성이 낮아질 수 있다.In the step (2), the temperature of the resultant product of step (1) is gradually raised to 60 to 150 ° C, preferably 80 to 130 ° C, and the internal electron donor is added during the temperature raising process to perform the reaction for 1 to 3 hours If the temperature is less than 60 ° C or the reaction time is less than 1 hour, the reaction is difficult to be completed. If the temperature exceeds 150 ° C or the reaction time exceeds 3 hours, the polymerization reaction of the resultant catalyst Or the stereoregularity of the polymer may be lowered.

상기 제1, 2 내부전자공여체는, 상기 승온과정 중에 투입되는 한, 그 투입 온도 및 투입 횟수는 크게 제한되지 않으며, 두 내부전자공여체를 동시에 혹은 다른 온도에서 주입하여도 무관하다. 상기 두 내부전자공여체의 전체 사용량에선 제한이 없으나 사용하는 두 내부전자공여체 전체의 몰수는 사용된 디알콕시마그네슘 1몰에 대하여 제1 내부전자공여체는 0.001~2.0몰을 제2 내부전자공여체는 0.001~2.0몰을 사용하는 것이 바람직한데, 상기 범위를 벗어나면, 결과물인 촉매의 중합활성 또는 중합체의 입체규칙성이 낮아질 수 있어 바람직하지 않다.As long as the first and second inner electron donors are charged during the temperature raising process, the charging temperature and the number of times of charging are not limited to a great extent, and two inner electron donors may be injected simultaneously or at different temperatures. The total amount of the two internal electron donors is not limited, but the total number of moles of the two internal electron donors used is 0.001 to 2.0 moles for the first internal electron donor and 0.001 to 2.0 moles for the second internal electron donor per mole of dialkoxymagnesium used. It is preferable to use 2.0 moles of the catalyst. Outside of the above range, the polymerization activity of the resultant catalyst or the stereoregularity of the polymer may be lowered.

상기 고체촉매의 제조공정 중 단계 (3)는, 60~150℃, 바람직하게는 80~130℃의 온도에서 단계 (2)의 결과물과 티타늄할라이드를 2차 이상 반응시키는 공정이다. 이때 사용되는 티타늄할라이드의 예로는 상기의 일반식(I)의 티타늄할라이드를 들 수 있다.The step (3) of the production of the solid catalyst is a step of reacting the result of step (2) with the titanium halide at a temperature of 60 to 150 ° C, preferably 80 to 130 ° C. An example of the titanium halide to be used at this time is titanium halide of the above-mentioned general formula (I).

고체촉매의 제조공정에 있어서, 각 단계에서의 반응은, 질소 기체 분위기에서, 수분 등을 충분히 제거시킨 교반기가 장착된 반응기 중에서 실시하는 것이 바람직하다.In the production process of the solid catalyst, the reaction in each step is preferably carried out in a reactor equipped with a stirrer in which water and the like are sufficiently removed in a nitrogen gas atmosphere.

상기와 같은 방법으로 제조되는 본 발명의 고체촉매는, 마그네슘, 티타늄, 할로겐, 실란계 화합물 및 내부전자공여체를 포함하여 이루어지며, 촉매 활성의 측면을 고려해 볼 때, 마그네슘 5~40중량%, 티타늄 0.5~10중량%, 할로겐 50~85중량%, 및 총내부전자공여체 2,5~30%이며, 이때 제1 내부전자공여체 0.1~20중량%, 제2 내부전자공여체 0.1 ~20중량%를 포함하여 이루어지는 것이 바람직하다. The solid catalyst of the present invention produced by the above method comprises magnesium, titanium, a halogen, a silane compound, and an internal electron donor. Considering the catalytic activity, the solid catalyst comprises 5 to 40% by weight of magnesium, 0.5 to 10% by weight of halogen, 50 to 85% by weight of halogen and 2,5 to 30% of total internal electron donors, wherein 0.1 to 20% by weight of the first internal electron donor and 0.1 to 20% by weight of the second internal electron donor .

본 발명의 촉매 제조방법에 의하여 제조되는 고체촉매는 프로필렌 중합 또는 공중합 방법에 적합하게 사용될 수 있으며, 본 발명에 의해 제조되는 고체촉매를 이용한 프로필렌 중합 또는 공중합 방법은 상기 고체촉매와 조촉매 및 외부전자공여체의 존재하에 프로필렌을 중합 또는 프로필렌과 다른 알파올레핀을 공중합시키는 것을 포함한다.The solid catalyst prepared by the catalyst preparation method of the present invention can be suitably used for the propylene polymerization or copolymerization method, and the propylene polymerization or copolymerization method using the solid catalyst produced by the present invention is characterized in that the solid catalyst, the cocatalyst, Polymerizing propylene in the presence of a donor or copolymerizing propylene with other alpha olefins.

상기 고체촉매는 중합 반응의 성분으로서 사용되기 전에 에틸렌 또는 알파올레핀으로 전중합하여 사용할 수 있다.The solid catalyst can be used in the prepolymerized state with ethylene or alpha olefin before being used as a component of the polymerization reaction.

전중합 반응은 탄화수소 용매(예를 들어, 헥산), 상기 촉매 성분 및 유기알루미늄 화합물(예를 들어, 트리에틸알루미늄)의 존재 하에서, 충분히 낮은 온도와 에틸렌 또는 알파올레핀 압력 조건에서 수행될 수 있다. 전중합은 촉매 입자를 중합체로 둘러싸서 촉매 형상을 유지시켜 중합 후에 중합체의 형상을 좋게 하는데 도움을 준다. 전중합 후의 중합체/촉매의 중량비는 약 0.1~20:1인 것이 바람직하다.The prepolymerization reaction can be carried out in the presence of a hydrocarbon solvent (e.g. hexane), the catalyst component and an organoaluminum compound (e.g. triethylaluminum) at sufficiently low temperatures and under ethylene or alpha olefin pressure conditions. Pre-polymerization helps encapsulate the catalyst particles in the polymer to maintain the shape of the catalyst to improve the shape of the polymer after polymerization. The weight ratio of polymer / catalyst after pre-polymerization is preferably about 0.1 to 20: 1.

상기 프로필렌 중합 또는 공중합 방법에서 조촉매 성분으로는 주기율표 제II족 또는 제III족의 유기금속 화합물이 사용될 수 있으며, 그 예로서, 바람직하게는 알킬알루미늄 화합물이 사용된다. 상기 알킬알루미늄 화합물은 일반식 (XI)로 표시된다:As the promoter component in the propylene polymerization or copolymerization method, an organometallic compound of Group II or Group III of the periodic table can be used, and as an example thereof, an alkyl aluminum compound is preferably used. The alkyl aluminum compound is represented by the general formula (XI): < EMI ID =

AlR3 ‥‥‥ (XI)AlR 3 (XI)

여기에서, R은 탄소수 1~6개의 알킬기이다. Here, R is an alkyl group having 1 to 6 carbon atoms.

상기 알킬알루미늄 화합물의 구체예로는, 트리메틸알루미늄, 트리에틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 트리이소부틸알루미늄 및 트리옥틸알루미늄 등을 들 수 있다.Specific examples of the alkylaluminum compound include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum and trioctylaluminum.

상기 고체촉매 성분에 대한 상기 조촉매 성분의 비율은, 중합 방법에 따라서 다소 차이는 있으나, 고체 촉매 성분 중의 티타늄 원자에 대한 조촉매 성분 중의 금속 원자의 몰비가 1~1000의 범위인 것이 바람직하며, 보다 바람직하게는 10~300의 범위인 것이 좋다. 만약, 고체촉매 성분 중의 티타늄 원자에 대한 조촉매 성분 중의 금속 원자, 예를 들어 알루미늄 원자의 몰비가 상기 1~1000의 범위를 벗어나게 되면, 중합 활성이 크게 저하되는 문제가 있다. The ratio of the cocatalyst component to the solid catalyst component varies depending on the polymerization method, but it is preferable that the molar ratio of metal atoms in the cocatalyst component to the titanium atom in the solid catalyst component is in the range of 1 to 1000, And more preferably in the range of 10 to 300. If the molar ratio of the metal atom in the cocatalyst component to the titanium atom in the solid catalyst component, for example, the aluminum atom, is out of the above range of 1 to 1000, the polymerization activity is greatly reduced.

상기 프로필렌 중합 또는 공중합 방법에서, 상기 외부전자공여체로는 다음의 일반식 (XII)로 표시되는 알콕시실란 화합물 중 1종 이상을 사용할 수 있다: In the propylene polymerization or copolymerization method, at least one of the alkoxysilane compounds represented by the following formula (XII) may be used as the external electron donor:

R1 mR2 nSi(OR3)(4-m-n) ‥‥‥ (XII) R 1 m R 2 n Si (OR 3 ) (4-mn) (XII)

여기에서, R1, R2은 동일하거나 다를 수 있으며, 탄소수 1~12개의 선형 또는 분지형 또는 시클릭 알킬기, 또는 아릴기이고, R3는 탄소수 1~6개의 선형 또는 분지형 알킬기이고, m, n은 각각 0 또는 1이고, m+n은 1 또는 2이다. Wherein R 1 and R 2 may be the same or different and are a linear or branched or cyclic alkyl group or an aryl group having 1 to 12 carbon atoms, R 3 is a linear or branched alkyl group having 1 to 6 carbon atoms, and m , n is 0 or 1, respectively, and m + n is 1 or 2.

상기 외부전자공여체의 구체예로는, 노르말프로필트리메톡시실란, 디노르말프로필디메톡시실란, 이소프로필트리메톡시실란, 디이소프로필디메톡시실란, 노르말부틸트리메톡시실란, 디노르말부틸디메톡시실란, 이소부틸트리메톡시실란, 디이소부틸디메톡시실란, 터셔리부틸트리메톡시실란, 디터셔리부틸디메톡시실란, 노르말펜틸트리메톡시실란, 디노르말펜틸디메톡시실란, 시클로펜틸트리메톡시실란, 디시클로펜틸디메톡시실란, 시클로펜틸메틸디메톡시실란, 시클로펜틸에틸디메톡시실란, 시클로펜틸프로필디메톡시실란, 시클로헥실트리메톡시실란, 디시클로헥실디메톡시실란, 시클로헥실메틸디메톡시실란, 시클로헥실에틸디메톡시실란, 시클로헥실프로필디메톡시실란, 시클로헵틸트리메톡시실란, 디시클로헵틸디메톡시실란, 시클로헵틸메틸디메톡시실란, 시클로헵틸에틸디메톡시실란, 시클로헵틸프로필디메톡시실란, 페닐트리메톡시실란, 디페닐디메톡시실란, 페닐메틸디메톡시실란, 페닐에틸디메톡시실란, 페닐프로필디메톡시실란, 노르말프로필트리에톡시실란, 디노르말프로필디에톡시실란, 이소프로필트리에톡시실란, 디이소프로필디에톡시실란, 노르말부틸트리에톡시실란, 디노르말부틸디에톡시실란, 이소부틸트리에톡시실란, 디이소부틸디에톡시실란, 터셔리부틸트리에톡시실란, 디터셔리부틸디에톡시실란, 노르말펜틸트리에톡시실란, 디노르말펜틸디에톡시실란, 시클로펜틸트리에톡시실란, 디시클로펜틸디에톡시실란, 시클로펜틸메틸디에톡시실란, 시클로펜틸에틸디에톡시실란, 시클로펜틸프로필디에톡시실란, 시클로헥실트리에톡시실란, 디시클로헥실디에톡시실란, 시클로헥실메틸디에톡시실란, 시클로헥실에틸디에톡시실란, 시클로헥실프로필디에톡시실란, 시클로헵틸트리에톡시실란, 디시클로헵틸디에톡시실란, 시클로헵틸메틸디에톡시실란, 시클로헵틸에틸디에톡시실란, 시클로헵틸프로필디에톡시실란, 페닐트리에톡시실란, 디페닐디에톡시실란, 페닐메틸디에톡시실란, 페닐에틸디에톡시실란 및 페닐프로필디에톡시실란 등이며, 이 중에서 1종 이상을 단독 또는 혼합하여 사용할 수 있다.Specific examples of the external electron donor include, but are not limited to, n-propyltrimethoxysilane, dinormalpropyldimethoxysilane, isopropyltrimethoxysilane, diisopropyldimethoxysilane, n-butylbutyltrimethoxysilane, dinormal butyldimethoxy Silane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, tertiarybutyltrimethoxysilane, ditertiarybutyldimethoxysilane, n-pentyltrimethoxysilane, dinormalpentyldimethoxysilane, cyclopentyltrimethoxy Silane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclohexyltrimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, , Cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cycloheptyltrimethoxysilane, dicycloheptyldimethoxysilane, cycloheptyl Methyldimethoxysilane, cycloheptylethyldimethoxysilane, cycloheptylpropyldimethoxysilane, cycloheptyldimethoxysilane, cycloheptyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylethyldimethoxysilane, phenylpropyldimethoxysilane, Propyltriethoxysilane, dinormalpropyldiethoxysilane, isopropyltriethoxysilane, diisopropyldiethoxysilane, n-butylbutyltriethoxysilane, dinormalbutyldiethoxysilane, isobutyltriethoxysilane, diisobutyl Diethoxy silane, tertiary butyl triethoxy silane, ditertiary butyl diethoxy silane, normal pentyl triethoxy silane, dinormal pentyl diethoxy silane, cyclopentyl triethoxy silane, dicyclopentyl diethoxy silane, cyclopentyl methyl Diethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylpropyldiethoxysilane, cyclohexyltriethoxysilane, dicyclohexyldiethoxysilane , Cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, cyclohexylpropyldiethoxysilane, cycloheptyltriethoxysilane, dicycloheptyldiethoxysilane, cycloheptylmethyldiethoxysilane, cycloheptylethyldiethoxysilane, cycloheptylethyldiethoxysilane, Phenyldiethoxysilane, phenylmethyldiethoxysilane, phenylethyldiethoxysilane, and phenylpropyldiethoxysilane. Of these, at least one of them may be used singly or in combination .

상기 고체촉매에 대한 상기 외부전자공여체의 사용량은 중합 방법에 따라서 다소 차이는 있으나, 촉매 성분 중의 티타늄 원자에 대한 외부전자공여체 중의 실리콘 원자의 몰비가 0.1~500의 범위인 것이 바람직하며, 1~100의 범위인 것이 보다 바람직하다. 만일, 상기 고체촉매 성분 중의 티타늄 원자에 대한 외부전자공여체 중의 실리콘 원자의 몰비가 0.1 미만이면 생성되는 프로필렌 중합체의 입체규칙성이 현저히 낮아져 바람직하지 않고, 500을 초과하면 촉매의 중합 활성이 현저히 떨어지는 문제점이 있다. Although the amount of the external electron donor to be used for the solid catalyst varies depending on the polymerization method, the molar ratio of the silicon atoms in the external electron donor to the titanium atom in the catalyst component is preferably in the range of 0.1 to 500, more preferably 1 to 100 Is more preferable. If the molar ratio of the silicon atom in the external electron donor to the titanium atom in the solid catalyst component is less than 0.1, the resulting stereoregularity of the resulting propylene polymer becomes significantly low, and if it exceeds 500, the polymerization activity of the catalyst is significantly reduced .

상기 프로필렌 중합 또는 공중합 방법에 있어서, 중합 반응의 온도는 20~120℃인 것이 바람직한데, 중합 반응의 온도가 20℃ 미만이면 반응이 충분하게 진행되지 못하여 바람직하지 않고, 120℃를 초과하면 활성의 저하가 심하고, 중합체 물성에도 좋지 않은 영향을 주므로 바람직하지 않다.In the above-mentioned propylene polymerization or copolymerization method, the polymerization reaction temperature is preferably 20 to 120 ° C. If the polymerization reaction temperature is less than 20 ° C, the reaction does not proceed sufficiently, which is undesirable. It is undesirable because it causes considerable deterioration and adversely affects the physical properties of the polymer.

본 발명은 폴리프로필렌 제조용 고체촉매의 제조방법에 대한 것으로써 디알콕시마그네슘을 금속할라이드와의 반응을 통해서 생성된 담체와 티타늄할라이드, 유기전자공여체 등으로 이루어진 고체촉매 제조방법 및 이를 이용한 폴리프로필렌 제조방법을 제공하는 것으로써, 특히 본 발명에 사용하는 2종의 유기전자공여체 중 카보닐기와 알콕시기가 포함된 내부전자공여체를 사용하는 것으로써 슬러리 중합법, 벌크중합법 또는 기상중합법 등의 다양한 형태의 프로필렌 중합공정에 적용이 가능하며, 높은 활성과 입체규칙성이 우수한 프로필렌 수지를 제조할 수 있다.The present invention relates to a process for producing a solid catalyst for the production of polypropylene, which comprises a solid catalyst prepared by reacting a dialkoxy magnesium with a metal halide, a titanium halide, an organic electron donor and the like, and a process for producing a polypropylene It is possible to use an internal electron donor containing a carbonyl group and an alkoxy group among the two types of organic electron donors used in the present invention to form various forms such as a slurry polymerization method, a bulk polymerization method and a gas phase polymerization method It is possible to produce a propylene resin which is applicable to a polymerization process of propylene and which is excellent in high activity and stereoregularity.

이하 실시예 및 비교예에 의해 본 발명을 상세히 설명하나, 이에 의해 본 발명이 한정되는 것은 아니다.
Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

실시예Example 1  One

1. 고체촉매의 제조 1. Preparation of solid catalyst

질소로 충분히 치환된 1리터 크기의 교반기가 설치된 유리반응기에 톨루엔 112ml와 디에톡시마그네슘(평균입경 20㎛인 구형이고, 입도분포지수가 0.86이고, 겉보기밀도가 0.35g/cc인 것) 15g을 투입하고 10℃로 유지하면서, 사염화티타늄 20ml를 톨루엔　30ml에 희석하여 1시간에 걸쳐 투입한 후, 반응기의 온도를 100℃까지 올려 주면서 디이소부틸프탈레이트 4.8g, 비시클로[2.2.1]헵탄-2,3-디카르복실산디페닐에스테르, 2.5g의 혼합물을 주입하였다. 100℃에서 2시간 동안 유지한 다음, 90℃로 온도를 내려 교반을 멈추고 상등액을 제거하고, 추가로 톨루엔 200ml를 사용하여 1회 세척하였다. 여기에 톨루엔 120ml와 사염화티타늄 20ml를 투입하여 온도를 100℃까지 올려 2시간 동안 유지하였으며, 이 과정을 1회 반복 수행하였다. 숙성과정이 끝난 상기의 슬러리 혼합물을 매회당 톨루엔 200ml로 2회 세척하고, 40℃에서 노말헥산으로 매회당 200ml씩 5회 세척하여 연노랑색의 고체촉매성분을 얻었다. 흐르는 질소에서 18시간 건조시켜 얻어진 고체촉매성분 중의 티타늄 함량은 2.0중량%였다.
To a glass reactor equipped with a stirrer having a volume of 1 liter sufficiently substituted with nitrogen, 112 ml of toluene and 15 g of diethoxy magnesium (sphere having an average particle size of 20 μm and a particle size distribution index of 0.86 and an apparent density of 0.35 g / cc) And 20 ml of titanium tetrachloride was diluted in 30 ml of toluene and added over 1 hour while maintaining the temperature at 10 캜. Then, while the temperature of the reactor was raised to 100 占 폚, 4.8 g of diisobutylphthalate, 5.0 g of bicyclo [2.2.1] heptane- , And 3-dicarboxylic acid diphenyl ester (2.5 g). The mixture was maintained at 100 DEG C for 2 hours, then cooled down to 90 DEG C, stirring was stopped, the supernatant was removed, and further washed once with 200 mL of toluene. 120 ml of toluene and 20 ml of titanium tetrachloride were added thereto, and the temperature was raised to 100 ° C and maintained for 2 hours. This procedure was repeated once. The aged slurry mixture thus obtained was washed twice with 200 ml of toluene per one time and washed with n-hexane at 40 ° C for five times with 200 ml each time to obtain a pale yellow solid catalyst component. The titanium content in the solid catalyst component obtained by flowing in flowing nitrogen for 18 hours was 2.0% by weight.

2. 폴리프로필렌 중합2. Polymerization of polypropylene

4리터 크기의 고압용 스테인레스제 반응기내에 상기의 고체촉매 10mg과 트리에틸알루미늄 10mmol, 디시클로펜틸메틸디메톡시실란 1mmol을 투입하였다. 이어서 수소 7000ml와 액체상태의 프로필렌 2.4L를 차례로 투입한 후, 온도를 70℃까지 올려서 중합을 실시하였다. 중합 개시 후 2시간이 경과하면 반응기의 온도를 상온까지 떨어뜨리면서 밸브를 열어 반응기 내부의 프로필렌을 완전히 탈기시켰다.10 mg of the above solid catalyst, 10 mmol of triethylaluminum and 1 mmol of dicyclopentylmethyldimethoxysilane were fed into a 4-liter high-pressure stainless steel reactor. Then, 7000 ml of hydrogen and 2.4 L of liquid propylene were added in turn, and the temperature was raised to 70 ° C to perform polymerization. After 2 hours from the start of the polymerization, the temperature of the reactor was dropped to room temperature, and the valve was opened to completely degas propylene inside the reactor.

그 결과 얻어진 중합체를 분석하여, 표 1에 나타냈다.The resulting polymer was analyzed and is shown in Table 1. < tb > < TABLE >

여기서, 촉매활성, 입체규칙성은 다음과 같은 방법으로 결정하였다.Here, the catalytic activity and stereoregularity were determined by the following method.

① 촉매활성(kg-PP/g-cat) = 중합체의 생성량(kg)÷촉매의 양(g)① Catalyst activity (kg-PP / g-cat) = amount of polymer produced (kg) ÷ amount of catalyst (g)

② 입체규칙성(X.I.): 혼합크실렌 중에서 결정화되어 석출된 불용성분의 중량%(2) Stereoregularity (XI): Weight% of insoluble matter crystallized and crystallized in mixed xylene

③ 용융흐름성(g/10 min): ASTM1238에 의해, 230℃, 2.16kg 하중에서 측정한 값(3) Melt flowability (g / 10 min): Measured by ASTM 1238 at 230 ° C under a load of 2.16 kg

④ 분자량분포(P.I.): 200℃의 온도에서 파라렐 플레이트 레오미터를 이용하여 얻어진 모듈러스 세퍼레이션 값으로부터 다음의 계산식을 이용하여 산출한 값④ Molecular weight distribution (P.I.): The value calculated from the modulus separation value obtained by using a paralle plate rheometer at a temperature of 200 ° C. using the following formula

P.I. = 54.6*(모듈러스 세퍼레이션)-1.76
PI = 54.6 * (modulus separation) -1.76

실시예Example 2 2

실시예 1의 1. 고체촉매의 제조에 있어서, 디이소부틸프탈레이트와 비시클로[2.2.1]헵탄-2,3-디카르복실산디페닐에스테르 혼합물 대신에 디이소부틸프탈레이트 3.9g을 주입후 승온하면서 40~60℃에서, 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1-메틸페닐)에스테르, 1.5g을 주입하여 촉매를 제조하였다. 고체촉매성분 중의 티타늄 함량은 1.9중량%였다. 다음으로, 실시예 1과 동일한 방법으로 폴리프로필렌 중합을 수행하고, 결과를 표 1에 나타냈다.
1. Preparation of the solid catalyst of Example 1 In the same manner as in Example 1 except that 3.9 g of diisobutyl phthalate was introduced instead of the mixture of diisobutyl phthalate and bicyclo [2.2.1] heptane-2,3-dicarboxylic acid diphenyl ester, 1.5 g of bicyclo [2.2.1] heptane-2,3-dicarboxylate (1-methylphenyl) ester was injected at 40 to 60 ° C to prepare a catalyst. The content of titanium in the solid catalyst component was 1.9% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.

실시예Example 3 3

실시예 1의 1. 고체촉매의 제조에 있어서, 디이소부틸프탈레이트와 비시클로[2.2.1]헵탄-2,3-디카르복실산디페닐에스테르의 혼합물 대신에 디이소부틸프탈레이트 4.0g, 7,7-디비시클로[2.2.1]헵탄-2,3-디카르복실산디(1,2-디-iso-프로필페닐)에스테르 1.8g의 혼합물을 사용하여 촉매를 제조하였다. 고체촉매성분 중의 티타늄 함량은 2.1중량%였다. 다음으로, 실시예 1과 동일한 방법으로 폴리프로필렌 중합을 수행하고, 결과를 표 1에 나타냈다.
Example 1 1. Preparation of solid catalyst In the same manner as in Example 1 except that 4.0 g of diisobutyl phthalate, 7 g of diisobutyl phthalate was used instead of the mixture of diisobutyl phthalate and bicyclo [2.2.1] heptane-2,3-dicarboxylic acid diphenyl ester, A mixture of 1.8 g of 7-dibicyclo [2.2.1] heptane-2,3-dicarboxylate di (1,2-di-isopropylphenyl) ester was used to prepare a catalyst. The content of titanium in the solid catalyst component was 2.1% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.

실시예Example 4 4

실시예 2의 고체촉매의 제조에 있어서, 디이소부틸프탈레이트와 비시클로[2.2.1]헵탄-2,3-디카르복실산디(1-메틸페닐)에스테르 대신에 디이소부틸프탈레이트 3.8g, 5,6-디메틸비시클로[2.2.1]헵트-5-엔-2,3-디카르복실산디페닐에스테르 2.1g를 각각 주입하여 촉매를 제조하였다. 고체촉매성분 중의 티타늄 함량은 2.0중량%였다. 다음으로, 실시예 1과 동일한 방법으로 폴리프로필렌 중합을 수행하고, 결과를 표 1에 나타냈다.
In the preparation of the solid catalyst of Example 2, 3.8 g of diisobutyl phthalate, 5 g of diisobutyl phthalate and 5 g of diisobutyl phthalate were used instead of diisobutyl phthalate and di (1-methylphenyl) ester bicyclo [2.2.1] heptane- And 2.1 g of 6-dimethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid diphenyl ester. The content of titanium in the solid catalyst component was 2.0% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.

실시예Example 5  5

1. 고체촉매의 제조 1. Preparation of solid catalyst

질소로 충분히 치환된 1리터 크기의 교반기가 설치된 유리반응기에 톨루엔 112ml와 디에톡시마그네슘(평균입경 20㎛인 구형이고, 입도분포지수가 0.86이고, 겉보기밀도가 0.35g/cc인 것) 15g을 투입하고 10℃로 유지하면서, 사염화티타늄 20ml를 톨루엔　30ml에 희석하여 1시간에 걸쳐 투입한 후, 반응기의 온도를 100℃까지 올려 주면서 디이소부틸프탈레이트 4.5g을 주입하였다. 100℃에서 2시간 동안 유지한 다음, 90℃로 온도를 내려 교반을 멈추고 상등액을 제거하고, 추가로 톨루엔 200ml를 사용하여 1회 세척하였다. 여기에 톨루엔 120ml와 사염화티타늄 20ml를 투입한 다음, N2,N2,N3,N3-테트라메틸비시클로[2.2.1]헵탄-2,3-디카르복스아마이드 1.8g을 주입한 다음 온도를 100℃까지 올려 2시간 동안 유지하였으며, 이 과정을 1회 반복 수행하였다. 숙성과정이 끝난 상기의 슬러리 혼합물을 매회당 톨루엔 200ml로 2회 세척하고, 40℃에서 노말헥산으로 매회당 200ml씩 5회 세척하여 연노랑색의 고체촉매성분을 얻었다. 흐르는 질소에서 18시간 건조시켜 얻어진 고체촉매성분 중의 티타늄 함량은 2.1중량%였다. 다음으로, 실시예 1과 동일한 방법으로 폴리프로필렌 중합을 수행하고, 결과를 표 1에 나타냈다.
To a glass reactor equipped with a stirrer having a volume of 1 liter sufficiently substituted with nitrogen, 112 ml of toluene and 15 g of diethoxy magnesium (sphere having an average particle size of 20 μm and a particle size distribution index of 0.86 and an apparent density of 0.35 g / cc) 20 ml of titanium tetrachloride was diluted in 30 ml of toluene while being kept at 10 ° C and added over 1 hour. Then, 4.5 g of diisobutylphthalate was added while raising the temperature of the reactor to 100 ° C. The mixture was maintained at 100 DEG C for 2 hours, then cooled down to 90 DEG C, stirring was stopped, the supernatant was removed, and further washed once with 200 mL of toluene. To this was added 120 ml of toluene and 20 ml of titanium tetrachloride and then 1.8 g of N 2 , N 2 , N 3 , N 3 -tetramethylbicyclo [2.2.1] heptane-2,3-dicarboxamide The temperature was raised to 100 < 0 > C and held for 2 hours, and this process was repeated once. The aged slurry mixture thus obtained was washed twice with 200 ml of toluene per one time and washed with n-hexane at 40 ° C for five times with 200 ml each time to obtain a pale yellow solid catalyst component. The titanium content in the solid catalyst component obtained by flowing in flowing nitrogen for 18 hours was 2.1% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.

비교예Comparative Example 1 One

실시예 1의 1. 고체촉매의 제조에 있어서, 디이소부틸프탈레이트 및 2-에톡시에틸 부틸레이트의 혼합물 대신에 디이소부틸프탈레이트 4.7g을 사용하여 촉매를 제조하였다. 고체촉매성분 중의 티타늄 함량은 2.6중량%였다. 다음으로, 실시예 1과 동일한 방법으로 폴리프로필렌 중합을 수행하고, 결과를 표 1에 나타냈다.
Example 1, 1. In the preparation of the solid catalyst, a catalyst was prepared using 4.7 g of diisobutyl phthalate instead of a mixture of diisobutyl phthalate and 2-ethoxyethyl butyrate. The titanium content in the solid catalyst component was 2.6% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.

비교예Comparative Example 2 2

1. 고체촉매의 제조1. Preparation of solid catalyst

질소로 충분히 치환된 1리터 크기의 교반기가 설치된 유리반응기에 톨루엔 150ml, 테트라하이드로퓨란 12ml, 부탄올 20ml, 마그네슘클로라이드 21g을 투입하고 110℃로 승온 후, 1시간을 유지시켜 균일 용액을 얻었다. 용액의 온도를 15℃로 냉각하고, 사염화티타늄　25ml를 투입한 후 반응기의 온도를 60℃에서 1시간에 걸쳐 승온하고, 10분 동안 숙성 후 15분간 정치시켜 담체를 가라앉히고, 상부의 용액을 제거하였다. 반응기 내에 남은 슬러리는 200ml의 톨루엔을 투입하고, 교반, 정치, 상등액 제거 과정을 2회 반복하여 세척하였다. 150 ml of toluene, 12 ml of tetrahydrofuran, 20 ml of butanol and 21 g of magnesium chloride were charged into a glass reactor equipped with a 1-liter stirrer sufficiently substituted with nitrogen, and the temperature was raised to 110 ° C and maintained for 1 hour to obtain a homogeneous solution. The temperature of the solution was cooled to 15 ° C and 25 ml of titanium tetrachloride was added. The temperature of the reactor was elevated at 60 ° C over 1 hour, aged for 10 minutes, allowed to stand for 15 minutes to allow the carrier to settle, Respectively. The remaining slurry in the reactor was charged with 200 ml of toluene and washed by repeating stirring, setting, and removal of the supernatant twice.

이렇게 얻어진 슬러리에 톨루엔 150ml를 주입한 후 15℃에서 사염화티타늄 25ml를 톨루엔 50ml에 희석하여 1시간에 걸쳐 투입한 후, 반응기의 온도를 30℃까지 분당 0.5℃의 속도로 올려 주었다. 반응 혼합물을 30℃에서 1시간 동안 유지한 다음, 디이소부틸프탈레이트 7.5ml를 주입하고, 다시 분당 0.5℃의 속도로　110℃까지 승온시켰다.　After 150 ml of toluene was poured into the slurry thus obtained, 25 ml of titanium tetrachloride was diluted with 50 ml of toluene at 15 ° C and added over 1 hour. The temperature of the reactor was increased to 30 ° C at a rate of 0.5 ° C per minute. The reaction mixture was maintained at 30 DEG C for 1 hour, then 7.5 mL of diisobutylphthalate was introduced, and the temperature was further raised to 110 DEG C at a rate of 0.5 DEG C per minute.

110℃에서 1시간 동안 유지한 다음, 90℃로 온도를 내려 교반을 멈추고 상등액을 제거하고, 추가로 톨루엔 200ml를 사용하여 동일한 방법으로 1회 세척하였다. 여기에 톨루엔 150ml와 사염화티타늄 50ml를 투입하여 온도를 110℃까지 올려 1시간 동안 유지하였다. 숙성과정이 끝난 상기의 슬러리 혼합물을 매회당 톨루엔　200ml로 2회 세척하고, 40℃에서 헥산으로 매회당 200ml씩 5회 세척하여 연노랑색의 고체촉매성분을 얻었다. 흐르는 질소에서 18시간 건조시켜 얻어진 고체촉매성분 중의 티타늄 함량은 3.3중량%였다.After maintaining at 110 DEG C for 1 hour, the temperature was lowered to 90 DEG C and stirring was stopped, and the supernatant was removed, and further washed once with 200 mL of toluene in the same manner. 150 ml of toluene and 50 ml of titanium tetrachloride were added thereto, and the temperature was elevated to 110 ° C and maintained for 1 hour. The aged slurry mixture was washed twice with 200 ml of toluene and washed with hexane (200 ml) at 40 캜 for 5 times each time to obtain a pale yellow solid catalyst component. The titanium content in the solid catalyst component obtained by drying in flowing nitrogen for 18 hours was 3.3% by weight.

활성
(g-PP/g cat 2h)activation
(g-PP / g cat 2h) X.I
(wt%)XI
(wt%) MI
(g/10min)MI
(g / 10 min) MWDMWD 실시예1Example 1 88,00088,000 99.499.4 2323 4.34.3 실시예2Example 2 87,00087,000 99.599.5 2525 4.24.2 실시예3Example 3 79,00079,000 99.499.4 3030 4.14.1 실시예4Example 4 77,00077,000 99.599.5 2727 4.34.3 실시예5Example 5 87,00087,000 99.599.5 2121 4.24.2 비교예1Comparative Example 1 71,00071,000 98.598.5 2727 4.14.1 비교예2Comparative Example 2 65,00065,000 98.198.1 3131 4.24.2

Claims (5)

티타늄;
마그네슘;
할로겐; 및
하기 일반식 (VI), (VII), (VIII), (IⅩ)로 표시되는 알릴기가 치환된 바이시클로알칸 및 알켄디카복스아마이드를 포함하는 내부전자공여체를 포함하는 것을 특징으로 하는 프로필렌 중합용 고체촉매:
Figure 112018043339049-pat00013
Figure 112018043339049-pat00014

Figure 112018043339049-pat00015
Figure 112018043339049-pat00016

여기에서, R11, R12, R13, R14, R15, 및 R16는 각각 독립적으로 탄소수 1∼12의 직쇄상 알킬기, 탄소수 3∼12의 분기 알킬기, 비닐기, 탄소수 3∼12의 직쇄상 알케닐기 또는 분기 알케닐기, 탄소수 1∼12의 직쇄상 할로겐 치환 알킬기, 탄소수 3∼12의 분기 할로겐 치환 알킬기, 탄소수 3∼12의 직쇄상 할로겐 치환 알케닐기 또는 분기 할로겐 치환 알케닐기, 탄소수 3∼12의 시클로알킬기, 탄소수 3∼12의 시클로알케닐기, 탄소수 3∼12의 할로겐 치환 시클로알킬기, 탄소수 3∼12의 할로겐 치환 시클로알케닐기, 또는 탄소수 6∼12의 방향족 탄화수소기이다.titanium;
magnesium;
halogen; And
A solid for propylene polymerization characterized by comprising an internal electron donor comprising an allyl substituted bicyclic alkane and alkenedicarboxamide represented by the following general formulas (VI), (VII), (VIII), (IX) catalyst:
Figure 112018043339049-pat00013
Figure 112018043339049-pat00014

Figure 112018043339049-pat00015
Figure 112018043339049-pat00016

Wherein each of R 11 , R 12 , R 13 , R 14 , R 15 and R 16 independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, A straight chain halogenated alkyl group having 1 to 12 carbon atoms, a branched halogenated alkyl group having 3 to 12 carbon atoms, a straight chain halogenated alkenyl group having 3 to 12 carbon atoms, or a branched halogenated alkenyl group having 3 to 12 carbon atoms, a straight chain alkenyl group having 3 to 12 carbon atoms, A cycloalkyl group having from 3 to 12 carbon atoms, a cycloalkenyl group having from 3 to 12 carbon atoms, a halogen-substituted cycloalkyl group having from 3 to 12 carbon atoms, a halogen-substituted cycloalkenyl group having from 3 to 12 carbon atoms, or an aromatic hydrocarbon group having from 6 to 12 carbon atoms. 제 1항에 있어서, 상기 고체촉매는 마그네슘 5~40중량%, 티타늄 0.5~10중량%, 할로겐 50~85중량% 및 총내부전자공여체 2.5~30중량%를 포함하는 것을 특징으로 하는 프로필렌 중합용 고체촉매.The process according to claim 1, wherein the solid catalyst comprises 5 to 40 wt% of magnesium, 0.5 to 10 wt% of titanium, 50 to 85 wt% of halogen, and 2.5 to 30 wt% of total internal electron donor Solid catalyst. 제 1항에 있어서, 상기 고체촉매는 알릴기가 치환된 바이시클로알칸 및 알켄디카복스아마이드를 포함하는 내부전자공여체 0.1~20중량%를 포함하는 것을 특징으로 하는 프로필렌 중합용 고체촉매.The solid catalyst for the polymerization of propylene according to claim 1, wherein the solid catalyst comprises 0.1 to 20% by weight of an internal electron donor comprising allyl-substituted bicycloalkane and alkenedicarboxamide. 제 1항에 있어서, 상기 고체촉매에 사용되는 2종의 내부전자공여체는 알릴기가 치환된 바이시클로알칸 및 알켄디카복스아마이드를 포함하는 내부전자공여체와 프탈산 에스테르 또는 1,3-디에테르계를 포함하는 것을 특징으로 하는 프로필렌 중합용 고체촉매.The method of claim 1, wherein the two internal electron donors used in the solid catalyst include an internal electron donor comprising an allyl substituted bicyclic alkane and an alkenedicarboxamide, and a phthalate ester or 1,3-diether system By weight based on the total weight of the solid catalyst. 제 1항 또는 제 2항에 따른 고체촉매와, 조촉매로서 AlR3(여기에서, R은 탄소수 1~6개의 알킬기이다) 및 외부전자공여체로서 R1 mR2 nSi(OR3)(4-m-n)(여기에서, R1과 R2는 동일하거나 다를 수 있으며, 탄소수 1~12개의 선형 또는 분지형 또는 시클릭 알킬기, 또는 아릴기이고, R3는 탄소수 1~6개의 선형 또는 분지형 알킬기이고, m, n은 각각 0 또는 1이고, m+n은 1 또는 2이다)의 존재하에 프로필렌을 중합, 또는 프로필렌과 다른 알파올레핀을 공중합시키는 것을 포함하는 폴리프로필렌 제조방법. A process for producing a solid catalyst according to any one of claims 1 to 3 , which comprises reacting AlR 3 (wherein R is an alkyl group having 1 to 6 carbon atoms) as a cocatalyst and R 1 m R 2 n Si (OR 3 ) (4 -mn wherein R 1 and R 2 may be the same or different and each is a linear or branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group and R 3 is a linear or branched An alkyl group, m and n are each 0 or 1, and m + n is 1 or 2, or copolymerizing propylene with other alpha olefins.
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KR20140001493A (en) * 2012-06-27 2014-01-07 삼성토탈 주식회사 A solid catalyst for propylene polymerization and a method for preparation of polypropylene
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KR20210047151A (en) * 2019-10-21 2021-04-29 한화토탈 주식회사 A solid catalyst for Polypropylene polymerization and a method for low Volatile organic compound
KR102259307B1 (en) 2019-10-21 2021-05-31 한화토탈 주식회사 A solid catalyst for Polypropylene polymerization and a method for low Volatile organic compound

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